Ester compound, agent for controlling noxious organisms containing the same as active ingredient, and production intermediate thereof

ABSTRACT

There is provided an ester compound represented by the formula I: ##STR1## wherein R 1  is a methyl group or a hydrogen atom; R 2  is a C 1-6  haloalkyl group; and R 3  is a pyrethroid acid residue, an agent for controlling noxious organisms containing the same as active ingredient and an intermediate for producing the same.

FIELD OF THE INVENTION

The present invention relates to an ester compound, an agent forcontrolling noxious organisms containing the same as an activeingredient, and a production intermediate thereof.

The present inventors have studied intensively in order to find acompound having an excellent effect for controlling noxious organisms.As a result, it has been found that an ester compound represented by thefollowing formula I has an excellent effect for controlling noxiousorganisms and, at the same time, an alcohol compound represented by theformula VII described hereinafter is a useful intermediate in theproduction of the ester compound, thus the present invention has beenaccomplished.

SUMMARY OF THE INVENTION

That is, the present invention provides an ester compound represented bythe formula I: ##STR2## wherein R₁ is a methyl group or a hydrogen atom;R₂ is a C₁₋₆ haloalkyl group; and R₃ is a pyrethroid acid residue (whichexcludes a carboxyl group) (hereinafter referred to as a "presentcompound"), an agent for controlling noxious insects containing the sameas an active ingredient and, a production intermediate thereof.

PREFERRED EMBODIMENT OF THE INVENTION

In the present compound I the C₁₋₆ haloalkyl group for R₂ includes, forexample, C₂₋₄ alkyl groups which may be substituted with a fluorine atomor atoms such as 2,2,2-trifluoroethyl group, 2,2-difluoroethyl group,pentafluoroethyl group, 2-fluoroethyl group and 3-fluoropropyl group.

The pyrethroid acid residue R₃ may be any residue that constitutes apyrethroid acid of an active pyrethroid ester insecticide and is notspecifically limited, and examples thereof include a group representedby the formula II: ##STR3## wherein Z₁ is a hydrogen atom or a methylgroup; and Z₂ is a hydrogen atom, a C₁ -C₆ alkyl group which may besubstituted with a halogen atom or atoms, a C₁ -C₆ alkoxy group whichmay be substituted with a halogen atom or atoms, a (C₁ -C₆ alkoxy)methylgroup which may substituted be with a halogen atom or atoms, a (C₁ -C₆alkoxy)ethyl group which may be substituted with a halogen atom oratoms, a C₂ -C₄ alkenyloxy group which maybe substituted with a halogenatom or atoms, a C₂ -C₄ alkynyloxy group which may be substituted with ahalogen atom or atoms, a. (C₂ -C₄ alkenyl)oxymethyl group which may besubstituted with a halogen atom or atoms or a (C₂ -C₄ alkynyl)oxymethylgroup which may substituted with a halogen atom or atoms;

Z₂ is a group of the formula III: ##STR4## wherein Z₃ is a hydrogen atomor a halogen atom; and T₁ and T₂ are the same or different and eachindicate a hydrogen atom, a halogen atom, a C₁ -C₃ alkyl group which maysubstituted with a halogen atom or atoms, a cyano group, a phenyl groupwhich may substituted with a halogen atom or atoms, a (C₁ -C₄alkoxy)carbonyl group which may substituted with a halogen atom oratoms, or T₁ and T₂ bond each other at their terminal and indicate a C₃-C₆ cycloalkyl group;

Z₂ is a group of the formula IV: ##STR5## wherein B is an oxygen atom ora sulfur atom; Z₂ is a group of the formula V: ##STR6## wherein D is ahydrogen atom or a halogen atom; and G is a C₁ -C₆ alkyl group which maybe substituted with a halogen atom or atoms, a C₃ -C₅ cycloalkyl groupor a phenyl group which may be substituted with a halogen atom or atoms;or

R₃ is a group of the formula VI: ##STR7## wherein J is a halogen atom; aC₁ -C₆ alkyl group which may be substituted with a halogen atom or atomsor a C₁ -C₆ alkoxy group which may be substituted with a halogen atom oratoms.

In the formulas for the present compound above, examples of the halogenatom include a fluorine atom, a chlorine atom and a bromine group, etc.,examples of the alkyl group include a methyl group, an ethyl group and apropyl group, etc., examples of the alkenyl group include an allylgroup, etc, examples of the alkynyl group include a propargyl group,etc., and examples of the alkoxy group include a methoxy, ethoxy andpropoxy group, etc.

For the group Z₂ in the formula II above, the C₁ -C₆ alkyl group whichmay be substituted with a halogen atom or atoms includes a methyl group,the C₁ -C₆ alkoxy group which may be substituted with a halogen atom oratoms includes C₂ -C₅ alkoxy groups such as a propoxy group, a butoxygroup, the C₂ -C₄ alkenyloxy group which may be substituted with ahalogen atom or atoms includes an allyloxy group, a C₂ -C₄ alkynyloxygroup which may be substituted with a halogen atom or atoms includes apropargyloxy group, the (C₂ -C₄ alkenyl)oxymethyl group which may besubstituted with a halogen atom or atoms includes an allyoxymethylgroup, and the (C₂ -C₄ alkynyl)oxymethyl group which may substitutedwith a halogen atom or atoms includes propargyloxymethyl group.

The C₃ -C₆ cycloalkyl group formed from T₁ and T₂ in formula IIIincludes a cyclopropyl group, a cyclobutyl group, a cyclopentyl group ora cyclohexyl group.

In Formula V the C₁ -C₆ alkyl group which may be substituted with ahalogen atom or atoms for G includes a C₁ -C₃ alkyl groups which may besubstituted with a fluorine atom or atoms, such as an ethyl group, etcand the C₃ -C₅ cycloalkyl group includes a cyclopropyl group etc.

For the group J in Formula VI the C₁ -C₆ alkyl group which may besubstituted with a halogen atom or atoms includes a trifluoromethylgroup, and difluoromethyl group, etc. and the C₁ -C₆ alkoxy group whichmay be substituted with a halogen atom or atoms includes atrifluoromethoxy group and a difluoromethoxy group, etc.

In the present compound, the C₁₋₆ haloalkyl groups for R₂ are preferablya C₂₋₄ alkyl group substituted with a fluorine atom or atoms, amongwhich a 2,2,2-trifluoroethyl group is particularly preferred.

In the present compound, when R₂ is a secondary C₁₋₆ haloalkyl group, R₁is pregerably a hydrogen atom, and when R₂ is a primary C₁₋₆ haloalkylgroup, R₁ is pregerably a methyl group.

In the present compound, preferred examples of the pyrethroid acidresidue represented by R₃ (which excludes a carboxyl group) include Q₁to Q₂₇ described in the formulas X and XI described hereinafter.

The present compound can be produced, for example, by the followingprocess.

Production process A

A process for producing the present compound, comprising reacting analcohol compound represented by the formula VII: ##STR8## wherein R₁ andR₂ are as defined above with a carboxylic acid represented by theformula VIII:

    R.sub.3 --COOH

wherein R₃ are as defined above or a reactive derivative thereof.

Examples of the reactive derivative of the carboxylic acid include acidhalide compounds, acid anhydrides and the like.

It is preferred that the reaction is conducted in an inert solvent inthe presence of a suitable condensing agent or a base, if necessary.Examples of the condensing agent include dicyclohexylcarbodiimide (DCC),1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (WSC) andthe like.

Examples of the base to be used include organic bases such astriethylamine, pyridine, 4-dimethylaminopyridine, diisopropylethylamineand the like. Examples of the solvent to be used include hydrocarbonssuch as benzene, toluene, hexane, etc.; ethers such as diethyl ether,tetrahydrofuran, etc.; halogenated hydrocarbons such as dichloromethane,1,2-dichloroethane, etc.

The reaction temperature can be preferably within a range from -20° C.to the boiling point of the solvent used for the reaction or 100° C.,more preferably from -5° C. to the boiling point of the solvent used forthe reaction or the temperature up to 100° C. The molar ratio of thealcohol compound represented by the formula VII to carboxylic acidrepresented by the formula VIII or the reactive derivative thereof to beused can be optionally set, but is advantageous to set at an equimolarratio or the ratio similar to the equimolar ratio. The condensing agentor base can be used in an amount within a range from an equimolar amountto an excessive amount, preferably from an equimolar amount to 5 molsbased on 1 mol of the alcohol compound of the formula VII.

After the completion of the reaction, the reaction solution can besubjected to a normal workup treatment such as extraction with organicsolvent, concentration, etc. to give the objective present compound. Ifnecessary, it may be purified by normal operations such aschromatography, distillation, recrystallization and/or the like.

The present compounds have stereoisomers (R/S) and geometrical isomers(cis/trans and E/Z), and all stereoisomers and geometrical isomers and amixture thereof which have an activity for controlling noxious organismsare included in the present invention.

In the above production process A, an optically active compound can beobtained from optically active materials without causing racemization,i.e. with retention of stereoisomerism.

In the production process A, examples of the alcohol compoundrepresented by the formula VII to be used as the raw compound includethe following compounds;

(RS)-3-(2-fluoroethyl)-2-methyl-4-oxo-2-cyclopentenol,

(S)-3-(2,2,2-trifluoroethyl)-2-methyl-4-oxo-2-cyclopentenol,

(RS)-3-(3,3-difluoropropyl)-2-methyl-4-oxo-2-cyclopentenol,

(RS)-3-(pentafluoroethyl)-2-methyl-4-oxo-2-cyclopentenol,

(RS)-3-(2,2,2-trifluoroethyl)-2-methyl-4-oxo-2-cyclopentenol,

(RS)-3-(3,3,3-trifluoropropyl)-2-methyl-4-oxo-2-cyclopentenol,

(RS)-3-(2,2-difluoroethyl)-2-methyl-4-oxo-2-cyclopentenol,

(RS)-3-(2-chloroethyl)-2-methyl-4-oxo-2-cyclopentenol,

(RS)-3-(2-chloro-2,2-difluoroethyl)-2-methyl-4-oxo-2-cyclopentenol.

The alcohol compound represented by the formula VII can be produced, forexample, according to the method described in Japanese Patent Kokai(Laid-open) No. 57-67537. More definitely, it can be produced, forexample, by the method shown in following reaction scheme IX. ##STR9##wherein R₁ and R₂ are as defined above.

Hereinafter, the processes [i] and [ii] will be explained.

Process (i): A ketocarboxylic acid compound represented by the formula[I] is reacted with a glyoxal derivative of the formula [II] in anaqueous alkaline solution or a mixed solvent of the aqueous alkalinesolution and an inert solvent at a temperature within a range normallyfrom 10° C. to a boiling point of the solvent to be used or 100° C.,preferably from 20° C. to a boiling point of the solvent to be used or100° C., for 10 minutes to 48 hours. It is advantageous to react thereaction solution at a pH range of from 7 to 9. Examples of the inertsolvent to be used optionally include ethers such as diethyl ether,tetrahydrofuran, etc.; halogenated hydrocarbons such as dichloromethane,etc.; hydrocarbons such as benzene, toluene, etc.

The molar ratio of the ketocarboxylic compound of the formula [I] toglyoxal derivative of the formula [II] to be used for the reaction canbe optionally set, but is advantageous to set at an equimolar ratio orthe ratio similar to the equimolar ratio.

Process (ii): After removing the solvent, the residue was reacted in anaqueous alkaline solution (pH is not less than 10, preferably 13 to 14)at a temperature within a range normally from -50° C. to 20° C.,preferably from -20° C. to 5° C. for 30 minutes to 48 hours. After thecompletion of the reaction, the reaction solution can be subjected to anormal workup such as extraction with organic solvent, concentration,etc. to isolate the objective compound. If necessary, it may be purifiedby normal operations such as chromatography, distillation and the like.

The ketocarboxylic acid compound represented by the formula [I] can beproduced, for example, by the method represented by the followingreaction scheme X. ##STR10## wherein R and R' are the same or differentand indicate a C₁₋₄ alkyl group (e.g. methyl group, ethyl group, etc.);and R₂ is as defined above.

Hereinafter, the processes (a) to (e) will be explained.

The step (a) of hydrolyzing an ester represented by the formula [IV] toproduce a carboxylic acid represented by the formula [V] will beexplained.

Usually, a base such as hydroxides of alkali metals (e.g. sodiumhydroxide, potassium hydroxide, etc.), hydroxides of alkali earth metals(e.g. barium hydroxide, etc.), carbonates of alkali metals (e.g.potassium carbonate, sodium carbonate, etc.) is used in an amount ofusually 1 to 10 equivalents, preferably 1.2 to 5 equivalents, based onthe amount of an ester of the formula [IV] and the base is reacted withthe ester in a protonic solvent (e.g. water, methanol, ethanol, ethyleneglycol, etc.) at a temperature within a range usually from -10° C. to aboiling point of the solvent to be used or 100° C., preferably from 0°C. to 50° C., for 30 minutes to 48 hours. After completion of thereaction, the reaction solution can be subjected to a normal workup suchas extraction With organic solvent, concentration, etc. to isolate theobjective present compound. If necessary, it may be purified by normaloperations such as distillation and the like.

Hereinafter, the process (b) of halogenating a carboxylic acidrepresented by the formula [V] to produce a carboxylic acid haliderepresented by the formula [VI] will be explained.

Usually, the carboxylic acid of the formula [V] is reacted with ahalogenating agent directly or in a hydrocarbon such as hexane, pentane,etc. Examples of the halogenating agent to be used include inorganicchlorides such as phosphoryl chloride, thionyl chloride, etc.; organicchlorides such as oxalic chloride, etc. If necessary, catalysts such aspyridine, triethylamine, N,N-dimethylformamide, hexamethylphosphorictriamide, etc. may be added in an amount of 0.01 to 1 mol, based on 1mol of the carboxylic acid of the formula [V]. The reaction temperaturemay be usually within a range from 0° C. to a boiling point of thesolvent to be used or 150° C. The molar ratio of the raw material andthe halogenating agent to be used for the reaction can be optionallyset, but is advantageous to set at an equimolar ratio or the ratiosimilar to the equimolar ratio. After the completion of the reaction,the reaction solution can be subjected to a normal workup-treatment suchas extraction with an organic solvent, concentration, etc. to isolatethe compound. If necessary, it may be purified by usual operations suchas distillation and the like.

Hereinafter, the process (c) of reacting the carboxylic acid haliderepresented by the formula [VI] with diethyl malonate to produce acompound represented by the formula [VII] will be explained.

Usually, the carboxylic acid halide of the formula [VI] is reacted withdiethyl malonate directly or in an inert solvent in the presence ofalcohols such as ethanol, methanol, etc. and suitable metals. Examplesof the metal to be used include alkaline earth metals such as magnesium,etc., alkaline metals such as lithium, etc. Examples of the solvent,used if nrcessary, include hydrocarbons such as benzene, xylene,toluene, etc. and ethers such as diethyl ether, tetrahydrofuran,dioxane, etc. The amount of the diethyl malonate, alcohol and metal canbe optionally-set, respectively, and they are preferably used in anamount of 1.2 to 5 equivalents, based on the amount of the carboxylicacid halide of the formula [VI], respectively. The reaction temperaturemay be usually within a range from -30° C. to a boiling point of thesolvent to be used or 150° C. After the completion of the reaction, thereaction solution can be subjected to a normal workup such as extractionwith organic solvent, concentration, etc. to isolate the objectivecompound. If necessary, it may be purified by normal operations such aschromatography, distillation, recrystallization and the like.

Hereinafter, the process (d) of hydrolyzing the compound represented bythe formula [VII], followed by decarboxylation to obtain a ketoestercompound represented by the formula [VIII] will be explained.

When the reaction is conducted under a basic condition, the ketoestercompound of he formula [VII] is usually reacted in protonic solventssuch as water, methanol, ethanol, ethylene glycol, etc. or a mixedsolvent thereof at a temperature within a range usually from 0° C. to aboiling point of the solvent to be used, preferably not less than 30° C.for 10 minutes to 48 hours in the presence of hydroxides of alkalinemetals, such as sodium hydroxide, potassium hydroxide, etc., hydroxidesof alkaline earth metals, such as barium hydroxide, etc., carbonates ofalkaline metals, such as potassium carbonate, sodium carbonate, etc. Themolar ratio of the raw material to the base to be used for the reactioncan be optionally set, but is advantageous to set at an equimolar ratioor the ratio similar to the equimolar ratio.

When the reaction is conducted under the acidic condition, the ketoestercompound of the formula [IV] is usually reacted in water or a mixedsolvent of water and alcohols (e.g. ethanol, methanol, etc.) or ethers(e.g. dioxane, tetrahydrofuran, etc.) at a temperature within a rangeusually from 0° C. to a boiling point of the solvent to be used,preferably not less than 30° C. for 10 minutes to 48 hours in thepresence of acids such as p-toluenesulfonic acid, trifluoroacetic acid,hydrochloric acid, etc. The molar ratio of the raw material and acid tobe used for the reaction can be optionally set, but is preferably usedin the amount of 0.0001 to 1 moles. After the completion of thereaction, the reaction solution can be subjected to a normal workup suchas extraction with organic solvent, concentration, etc. to isolate theobjective compound. If necessary, it may be purified by normaloperations such as chromatography, distillation and the like.

The process (e) of hydrolyzing a ketoester compound of the formula[VIII] to produce a ketocarboxylic compound represented by the formula[I] can be conducted according to the same manner as that described inthe process (a).

Examples of noxious insects against which the present compound exhibitsa control effect include the followings:

Hemiptera:

Delphacidae (planthoppers) such as Laodelphax striatellus, Nilaparvatalugens and Sogatella furcifera; Cicadelloidea (leafhoppers) such asNephotettix cincticeps, Recilia dorsalis and Nephotettix virescens,Aphidoidea (aphids), plant bugs such as Pentatomidae, Coreidae,Alydidae, Tingidae (lace bugs), and Miridae, Aleyrodidae, Coccoidea(scale insects), Psyllidae (jumping plant lice), etc.;

Lepidoptera:

Pyralidae such as Chilo suppressalis and Cnaphalocrocis medinalis,Noctuidae (owlet moths) such as Spodoptera litura, Pseudaletia separata,and Mamestra brassicae, Heliothis moths, Agrotis moths such as Agrotisipsilon and Agrotis segetum (turnip moth), Pieridae such as Pieris rapaecrucivora, Tortricidae (bell moths), carposinidae, Lyonetiidae,Lymantriidae, Plutella xylostella, Tinea translucens, Tineolabisselliella, etc.;

Diptera:

Culex (house mosquitos) such as Culex pipiens pallens and Culextritaeniorhynchus, Aedes such as Aedes albopictus and Aedesaegypti,Anopheles such as Anopheles sinensis, Chironomidae (midges),Muscidae such as Musca domestica (house fly) and Muscina stabulans,Fannia canicularis, Calliphoribae (blow flies), Sarcophagidae (fleshflies), Anthomyiidae such as Delia Platura and Delia antiqua,Tephritidae (fruit flies), Drosophilidae, Psychodidae (moth flies),Tabanidae (deer flies), Simuliidae (black flies), Stomoxyidae, etc.;

Coleoptera (beetles):

Diabrotica (corn rootworms) such as Diacrotica virgifera and Diabroticaundecimpunctata, Scarabaeidae such as Anomala cuprea and Anomalarufocuprea, Curculionidae (snout beetles) such as Sitophilus zeamais(grain weevils) and Lissorhoptrus oryzophilus, Tenebrionidae (darklingbeetles) such as Neatus ventralis, Tenebrio molitor and Triboliumcastaneum, Chrysomelidae (leaf beetles) such as Aulacophora femoralisand Phyllotreta striolata, Anobiidae (death-watch beetles),Coccinellidae (ladybird beetles) such as Epilachna vigintioctopunctata,Lyctidae (powder-post beetles), Bostrychidae Cerambycidae, Paederusfuscipes, etc.;

Blattaria (cockroaches):

Blattella germanica, Periplaneta fuliginosa, Periplaneta americana,Periplaneta brunnea, Blatta orientalis, etc.;

Thysanoptera (thrips):

Thrips palmi, Thrips tabaci, Thrips hawaiiensis, etc.;

Hymenoptera:

Formicidae (ants), Vespidae (hornets), Bethylidae (bethylid wasps),Tenthredinidae (sawflies) such as Athalia japonica (cabbage sawfly),etc.;

Orthoptera:

Gryllotalpidae (mole crickets), Acrididae (grasshoppers), etc.;

Siphonaptera (fleas):

Purex irritans, etc.;

Anoplura (sucking lice):

Pediculus humanus, Pthirus pubis, etc.;

Isoptera (termites):

noxious insects such as Reticulitermes speratus, Coptotermes formosanus,etc.;

Tetranychidae (spider mites):

Tetranychus cinnabarinus, Tetranychus urticae, Tetranychus kanzawai,Panonychus citri, Panonychus ulmi, etc.;

Ixodidae (ticks):

Boophilus microplus;

House dust mites:

noxious mites such as Acaridae, Pyroglyphidae, Cheyletidae,Macronyssidae, etc.;

Nematoda (soil nematodes):

root-lesion nematodes, cyst nematodes, root-knot nematodes, etc.; and

Nematoda (nematodes):

Bursaphelenchus xylophilus (pine wood nematode), etc.

When the present compound is used as an active ingredient of an agentfor controlling noxious organisms, it is usually mixed with solidcarriers, liquid carriers, gaseous carriers, baits, etc. to formulate.Alternatively, a base material of a mosquito-coil or an electricmosquito-mat for electric heating fumigation is impregnated with thepresent compound. Surfactants and other auxiliary agents for formulationmay be optionally added to the present compound. Examples of theformulation for the present compound include oil solutions, emulsifiableconcentrates, wettable powders, flowables such as water suspensions andemulsions, granules, dusts, aerosols, heating smoke formulations such asmosquito-coils, mosquito-mats, or non-mats for electric heatingfumigation, self-combustion type smoke formulations, chemical reactiontype smoke formulations, heating smoke formulations such as a porousceramic fumigant, non-heating transpiration formulations such asvolatile agents applied on resin or paper, fogging agents, ULV agents,poison bait and the like.

These formulations usually contain the present compound as the activeingredient in an amount of 0.001 to 95% by weight.

Examples of the solid carrier used for the preparation include finepowders or particulates such as clays (e.g. kaolin clay, diatomaceousearth, synthetic hydrated siliconoxide, bentonite, Fubasami clay, acidclay, etc.), talcs, ceramics, other inorganic minerals (e.g. sericite,quartz, sulfur, active carbon, calcium carbonate, hydrated silica,etc.), commercial fertilizers (e.g. ammonium sulfate, ammoniumphosphate, ammonium nitrite, urea, ammonium chloride, etc.). Examples ofthe liquid carrier include water, alcohols (e.g. methanol, ethanol,etc.), ketones (e.g. acetone, methyl ethyl ketone, etc.), aromatichydrocarbons (e.g. benzene, toluene, xylene, ethylbenzene,methylnaphthalene, etc.), aliphatic hydrocarbons (e.g. hexane,cyclohexane, kerosine, gas oil, etc.), esters (e.g. ethyl acetate, butylacetate, etc.), nitriles (e.g. acetonitrile, isobutylonitrile, etc.),ethers (e.g. diisopropyl ether, dioxane, etc.), acid amides (e.g.N,N-dimethylformamide, N,N-dimethylacetamide, etc.), halogenatedhydrocarbons (e.g. dichloromethane, trichloroethane, carbontetrachloride, etc.), dimethyl sulfoxide, vegetable oils (e.g. soybeanoil, cottonseed oil, etc.) and the like. Examples of the gaseouscarrier, i.e. propellent include flon gas, butane gas, LPG (liquefiedpetroleum gas), dimethyl ether, carbon dioxide gas and the like.

Examples of the surfactant include alkyl sulfate, alkyl sulfonate, alkylaryl sulfonate, alkyl aryl ethers and polyoxyethylene alkyl aryl ether,polyoxyethylene glycol ethers, polyhydroxy alcohol esters, sugar alcoholderivatives and the like.

Examples of the auxiliary agent for formulation include stickers anddispersants, such as casein, gelatin, polysaccharides (e.g. starch, gumarabic, cellulose derivative, alginic acid, etc.), lignin derivatives,bentonite, saccharides, synthetic water-soluble polymers (e.g. polyvinylalcohol, polyvinyl pyrrolidone, polyacrylic acids, etc.). Examples ofthe stabilizer include PAP (acid isopropyl phosphate), BHT(2,6-di-tert-butyl-4-methylphenol), BHA (mixture of2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol),vegetable oils, mineral oils, surfactants, fatty acids or estersthereof.

Examples of the base material of the mosquito-coils include a mixture ofwood powder such as pyrethrum marc, powder of Machilus thunbergii siebet Zucc. and a binding agent like starch or gluten.

Examples of the base material of the mosquito-mat for electric heatingfumigation include a plate of compacted fibrils of cotton linters or amixture of pulp and cotton linters

Examples of the base material of the self-combustion type smokeformulation include combustion exothermic agents (e.g. nitrate, nitrite,guanidine salt, potassium chlorate, nitrocellulose, ethyl cellulose,wood flour, etc.), pyrolysis stimulants (e.g. alkaline metal salt,alkaline earth metal salt, bichromate, chromate, etc.), oxygen suppliers(e.g. potassium nitrate, etc.), a combustion assistant (e.g. melamine,wheat starch, etc.), bulking agents (e.g. diatomaceous earth, etc.),binders (e.g. synthetic starch, etc.) and the like.

Examples of the base material of the chemical reaction type smokeformulation include exothermic agents (e.g. sulfide, polysulfide, watersulfide and hydrated salt of alkali metal, calcium oxide, etc.),catalysts (e.g. carbonaceous substance, iron carbide, activated clay,etc.), organic foaming agents (e.g. azodicarbonamide, benzenesulfonylhydrazide, dinitrosopentamethylenetetramine, polystyrene, polyurethane,etc.), fillers (e.g. natural fiber fragment, synthetic fiber fragment,etc.) and the like.

Examples of the base material of non-heating transpiration formulationinclude thermoplastic resin, filter paper, Japanese paper and the like.

Examples of the base material of the poison bait include bait componentssuch as grain powder, vegetable oil, sugar, crystalline cellulose, etc.;antioxidants such as dibutylhydroxytoluene, nordihydrogualaretic acid,etc.; preservatives such as dehydroacetic acid, etc.; substances forpreventing erroneous ingestion such as red pepper powder, etc.;attractant flavors such as cheese flavor, onion flavor, peanut oil, etc.

Flowables (water suspension or emulsion) can be obtained by finelydispersing 1 to 75% by weight of the compound as an active ingredient inwater containing 0.5 to 15% by weight of a dispersing agent, 0 to 10% byweight of a suspension auxiliary (e.g. protective colloid, compoundimparting thixotropic properties, etc.) and 0 to 10% by weight of anauxiliary agent (e.g. defoamer, rust preventive, stabilizer, spreadingagent, penetration auxiliary, antifreezing agent, antibacterial agent,antifungal substance, etc.). It is also possible to formulate into asuspension in oil by using an oil in which the compound is hardlydissolved in place of water. As the protective colloid, for example,there can be used gelatin, casein, gums, cellulose ether, polyvinylalcohol and the like. Examples of the compound imparting thixotropicproperties include bentonite, aluminum magnesium silicate, xanthangum,polyacrylic acid and the like.

The formulation thus obtained is used as prepared or after diluted withwater. The formulations may be used after mixed with other insecticides,acaricides, nematicides, soil insect pest control agents, fungicides,herbicides, plant growth regulators, synergists, fertilizers, soilconditioners and the like, or used simultaneously with them.

Examples of the insecticide, nematicide and acaricide includeorganophosphorous compounds such as fenitrothion [O,O-dimethylO-(3-methyl-4-nitrophenyl) phosphorothioate], fenthion [O,O-dimethylO-(3-methyl-4-(methylthio)phenyl)phosphorothioate], diazinon[O,O-diethyl-O-2-isopropyl-6-methylpyrimidin-4-ylphosphorothioate]chlorpyriphos [O,O-diethyl-O-3,5,6-trichloro-2-pyridylphosphorothioate], acephate [O,S-dimethylacetyl phosphoramidothioate],methidathione[S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazole-3-ylmethylO,O-dimethylphosphorodithioate], disulfoton [O,O-diethylS-2-ethylthioethyl phosphorothioate], DDVP [2,2-dichlorovinyldimethylphosphate], sulprofos [O-ethyl O-4-(methylthio) phenyl S-propylphosphorodithioate], cyanophos [O-4-cyanophenylO,O-dimethylphosphorothioate], dioxabenzofos[2-methoxy-4H-1,3,2-benzodioxaphosphorin-2-sulfide], dimethoate[O,O-dimethyl-S-(N-methylcarbamoylmethyl) dithiophosphate], phenthoate[ethyl 2-dimethoxyphosphinothioylthio(phenyl) acetate], malathion[diethyl (dimethoxyphosphinothioylthio) succinate], trichlorfone[dimethyl (2,2,2-trichloro-1-hydroxyethyl)phosphonate], azinphos-methyl[S-(3,4-dihydro-4-oxo-1,2,3-benzotriazine-3-ylmethyl) O,O-dimethylphosphorodithioate], monocrotophos[dimethyl-(E)-1-methyl-2-(methylcarbamoyl) vinyl phosphate], and ethion[O,O,O',O'-tetraethyl S,S'-methylenebis(phosphorodithioate)].

Other examples are carbamate compounds such as BPMC [2-sec-butylphenylmethylcarbamate], benfuracarb [ethylN-(2.3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl(methyl)aminothio]-N-isopropyl-β-alaninate], propoxur[2-isopropoxyphenyl N-methylcarbamate], carbosulfan[2,3-dihydro-2,2-dimethyl-7-benzo[b]furanyl N-dibutylaminothio-N-methylcarbamate], carbaryl [1-naphthyl-N-methylcarbamate], methomyl[S-methyl-N-((methylcarbamoyl)oxy, thioacetoimidate], ethiofencarb[2-(ethylthiomethyl)phenyl methyl carbamate], aldicarb[2-methyl-2-(methylthio) propanaldehyde O-(methylcarbamoyloxime)],oxamyl [N,N-dimethyl-2-methylcarbamoyloxyimino-2-(methylthio)acetamide],and fenothiocarb [S-4-phenoxybutyl)-N,N-dimethylthiocarbamate].

Other examples include pyrethroid compounds such as etofenprox[2-(4-ethoxyphenyl)-2-methylpropyl-3-phenoxybenzyl ether], fenvalerate[(RS)-α-cyano-3-phenoxybenzyl (RS)-2-(4-chlorophenyl)-3-methylbutyrate],es-fenvalerate [(S)-α-cyano-3-phenoxybenzyl(S)-2-(4-chlorophenyl)-3-methylbutyrate], fenpropathrin[(RS)-α-cyano-3-phenoxybenzyl2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin[(RS)-α-cyano-3-phenoxybenzyl(1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],permethrin [3-phenoxybenzyl(1RS)-cis,trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],cyhalothrin [(RS)-α-cyano-3-phenoxybenzyl(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate],deltamethrin [(S)-α-cyano-3-phenoxybenzyl(1R)-cis-3-(2,2-dibromovinyl)-2,2-dimethylcyclopropanecarboxylate],cycloprothrin [(RS)-α-cyano-3-phenoxybenzyl(RS)-2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylate],fluvalinate [α-cyano-3-phenoxybenzylN-(2-chloro-α,α,α-trifluoro-p-tolyl)-D-valinate), bifenthrin[2-methylbiphenyl-3-ylmethyl)(Z)-(1RS)-cis-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate,2-methyl-2-(4-bromodifluoromethoxyphenyl) propyl (3-phenoxybenzyl)ether, tralomethrin [(1R-cis) 3 {(1'RS(1',2',2',2'-tetrabromoethyl)}-2,2-dimethylcyclopropanecarboxylic acid(S)-α-cyano-3-phenoxybenzyl ester], silafluofen [4-ethoxyphenyl{3-(4-fluoro-3-phenoxyphenyl) propyl} dimethylsilane], d-phenothrin[3-phenoxybenzyl (1R-cis,trans)-chrysantemate], cyphenothrin[(RS)-α-cyano-3-phenoxybenzyl (1R-cis,trans)-chrysanthemate],d-resmethrin [5-benzyl-3-furylmethyl (1R-cis,trans)-chrysanthemate],acrinathrin [(S)-α-cyano-3-phenoxybenzyl (1R-cis(Z))-(2,2-dimethyl-3-{3-oxo-3-(1,1,1,3,3,3-hexafluoropropyloxy)propenyl} cyclopropanecarboxylate], cyfluthrin[(RS)-α-cyano-4-fluoro-3-phenoxybenzyl3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate], tefluthrin[2,3,5,6-tetrafluoro-4-methylbenzyl(1RS-cis(Z))-3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylate],transfluthrin [2,3,5,6-tetrafluorobenzyl(1R-trans)-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate],tetramethrin [3,4,5,6-tetrahydrophthalimidomethyl(1RS)-cis,trans-chrysanthemate], allethrin[(RS)-3-allyl-2-methyl-4-oxocyclopent-2-enyl(1RS)-cis,trans-chrysanthemate], prallethrin[(S)-2-methyl-4-oxo-3-(2-propynyl)cyclopent-2-enyl(1R)-cis,trans-chrysanthemate], empenthrin[(RS)-1-ethynyl-2-methyl-2-pentenyl (1R)-cis,trans-chrysanthemate],imiprothrin [2,5-dioxo-3-(prop-2-ynyl)imidazolidin-1-ylmethyl(1R)-cis,trans-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropanecarboxylate], d-furamethrin [5-(2-propynyl) furfuryl(1R)-cis,trans-chrysanthemate], and 5-(2-propynyl)-furfuryl2,2,3,3-tetramethylcyclopropanecarboxylate.

Other examples include thiadiazine derivatives such as buprofezin(2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-thiadiazinan-4-one),nitroimidazolidine derivatives such as Imidacloprid(1-(6-chloro-3-pyridylmethyl)-N-nitroimidazolidin-2-ylindenamine],nereistoxin derivatives such as cartap[S,S'-(2-dimethylaminotrimethylene)bis(thiocarbamate)], thiocyclam[N,N-dimethyl-1,2,3-trithian-5-ylamine] and Bensultap[S,S'-2-dimethylaminotrimethylenedi (benzenethiosulfonate)],N-cyanoamidine derivatives such asN-cyano-N'-methyl-N'-(6-chloro-3-pyridylmethyl)acetoamidine; chlorinatedhydrocarbons such as endosulfan[6,7,8,9,10,10-hexachloro-1,5,5a,6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin-3-oxide],γ-BHC [1,2,3,4,5,6-hexachlorocyclohexane],1,1-bis(chlorophenyl)-2,2,2-trichloroethanol, benzoylphenylureacompounds such as chlorfluazuron[1-(3,5-dichloro-4-(3-chloro-5-trifluoromethylpyridine-2-yloxy)phenyl)-3-(2,6-difluorobenzoyl) urea, teflubenzuron[1-(3,5-dichloro-2,4-difluorophenyl)-3-(2,6-difluorobenzoyl) urea], andfulphenoxron[1-(4-(2-chloro-4-trifluoromethylphenoxy)-2-fluorophenyl]-3-(2,6-difluorobenzoyl)urea], formamidine derivatives such as amitraz [N,N' [(methylimino)dimethylidine] di-2,4-xylidine], chlorodimeform[N'-(4-chloro-2-methylphenyl)-N,N-dimethylmethinimidamide]; thioureaderivatives such as diafenthiuron[N-(2,6-diisopropyl-4-phenoxyphenyl)-N'-tert-butylcarbodiimide];phenylpyrazole compounds such as bromopropylate [isopropyl4,4'-dibromobenzilate], tetradifon [4-chlorophenyl 2,4,5-trichlorophenylsulfone], quinomethionate[S,S-6-methylquinoxaline-2,3-diyldithiocarbonate], propargite[2-(4-tert-butylphenoxy)cyclohexyl prop-2-yl sulfate], fenbutatin oxide[bis(tris(2-methyl-2-phenylpropyl]tin]oxide, hexythiazox[(4RS,5RS)-5-(4-chlorophenyl)-N-chlorohexyl-4-methyl-2-oxo-1,3-thiazolidine-3-carboxamide],chlofentezine [3,6-bis(2-chlorophenyl)-1,2,4,5-tetrazine], pyridathioben[2-tert-butyl-5-(4-tert-butylbenzylthio)-4-chloropyridazin-3(2H)-one],phenypyroxymate [tert-butyl(E)-4-[(1,3-dimethyl-5-phenoxypyrazole-4-yl)methyleneaminotoxymethyl] benzoate], debphenpyrad[4-N-tert-butylbenzyl)-4-chloro-3-ethyl-1-methyl-5-pyrazol carboxamide];polynactin complexes including tetranactin, trinactin and dinactin,milbemectin, avermectin, ivermectin, azadilactin [AZAD], pyrimidifen[5-chloro-N-[2-{4-(2-ethoxyethyl)-2,3-dimethylphenoxy}ethyl]-6-ethylpyrirnidine-4-amine, fipronil [1H-pyrazole-3-carbonitrile-5-amino-1-{2,6-dichloro-4-(trifluoromethyl)phenyl}-4-{(trifluoromethyl)sulfinyl}]; methoxaziazone[5-methoxy-3-(2-methoxyphenyl)-1,3,4-oxadiazol-2(3H)-one].

When the present compound is used as an active ingredient of an agentfor controlling noxious organisms for agricultural use, its applicationrate is usually 5 to 500 g per 10 ares. Emulsifiable concentrates,wettable powders and flowables are usually diluted with water to theconcentration of 0.1 to 1000 ppm. Granules and dusts are applied asprepared. When the present compound is used as an active ingredient ofan agent for controlling noxious organisms; for household useemulsifiable concentrates, wettable powders and flowables are usuallydiluted with water to the concentration of 0.1 to 1000 ppm. Oilsolutions, aerosols, fumigants, smoke formulations, transpirationformulations, fog formulations, ULV formulations, poison baits, etc. areapplied as prepared.

The application rate and a concentration of the formulations may bevaried, i.e., optionally increased or decreased according to the type offormulation, time, place and method of application, kind of noxiousinsect, degree of damage and the like.

The following Preparation Examples, Formulation Examples and TestExamples further illustrate the present invention in detail but are notto be construed to limit the scope thereof.

First, Production Examples of the present compound will be described.

Preparation Example 1

To a mixed solution of 300 mg of(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxocyclopent-2-en-1-ol, 5 mg of2,6-di-tert-butyl-4-methylphenol, 185 mg of pyridine, 5 mg of4-dimethylaminopyridine and 8 ml of dried tetrahydrofuran, 422 mg of(1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acidchloride was added under ice cooling, and the mixture was furtherreacted at room temperature for 8 hours. Thereafter, 10 ml of an aqueous10% ammonia solution was added to the reaction solution, followed bystirring vigorously for 2 hours. The reaction solution was extractedthree times with diethyl ether and the layer were combined. Then, thecombined ether layer was washed with saturated saline and dried overanhydrous magnesium sulfate, and the solvent was distilled off underreduced pressure. The residue was subjected to silica gel columnchromatography (eluent: mixture of n-hexane and ethyl acetate (30:1)containing 0.1% 2,6-di-tert-butyl-4-methylphenol) to give 460 mg of(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxo-2-cyclopenten-1-yl(1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate(compound 5) (yield: 77%).

n_(D) ²⁵ 1.4915 ¹ H-NMR (CDCl₃, inter standard TMS) δ value (ppm) 1.21(m, 3H), 1.35 (m, 3H), 1.63 (m, 1H), 2.12 (d, 3H), 2.35 (m, 2H), 2.76(m, 1H), 3.12 (q, 2H), 5.62 (m, 1H), 5.76 (brd, 0.5H), 5.85 (brd, 0.5H)

Preparation Example 2

To a mixed solution of 300 mg of(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxocyclopent-2-en-1-ol, 5 mg of2,6-di-tert-butyl-4-methylphenol, 185 mg of pyridine, 5 mg of4-dimethylaminopyridine and 8 ml of dried tetrahydrofuran, 425 mg of2,2,3,3-tetramethylcyclopropanecarboxylic acid chloride (70% (w/w)toluene solution) was added dropwise under ice cooling, and the mixturewas continuously reacted at room temperature for 6 hours. Thereafter, 10ml of an aqueous 10% ammonia solution was added to the reactionsolution, followed by stirring vigorously for 2 hours. The reactionsolution was extracted three times with diethyl ether and the layerswere combined. Then, the combined ether layer was washed with saturatedsaline and dried over anhydrous magnesium sulfate, and the solvent wasdistilled off under reduced pressure. The residue was subjected tosilica gel column chromatography (eluent: mixture of n-hexane and ethylacetate (30:1)containing 0.1% 2,6-di-tert-butyl-4-methylphenol) to give275 mg of(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxo-2-cyclopenten-1-yl2,2,3,3-tetramethylcyclopropanecarboxylate (compound 9) (yield: 56%).

n_(D) ²⁵ 1.4621 ¹ H-NMR (CDCl₃, internal standard TMS) δ value (ppm)1.23 (m, 13H), 2.11 (s, 3H), 2.32 (dd, 1H), 2.92 (dd, 1H), 3.10 (q, 2H),5.73 (brd, 1H) ¹⁹ F-NMR (CDCl₃, internal standard CCl₃ F) δ value (ppm)-64.95 (t, 3F)

Preparation Example 3

To a mixed solution of 300 mg of(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxocyclopent-2-en-1-ol, 5 mg of2,6-di-tert-butyl-4-methylphenol, 183 mg of pyridine and 7 ml oftoluene, 270 mg of(1R)-trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylicacid chloride was added dropwise under ice cooling, and the mixture wasfurther reacted at room temperature for 8 hours. The reaction solutionwas poured into a 5% ice-cooled citric acid solution, and extractedthree times with diethyl ether. The layers were combined and thecombined ether layer was washed in turn with an aqueous saturated sodiumbicarbonate and saturated saline. After drying over anhydrous magnesiumsulfate, the solvent was distilled off under reduced pressure. Theresidue was subjected to silica gel chromatography (eluent: mixture ofn-hexane and ethyl acetate (30:1) containing 0.1%2,6-di-tert-butyl-4-methylphenol) to give 330 mg of(RS)-2-methyl-4-oxo-3-(2,2,2-trifluoroethyl)-2-cyclopenten-1-yl(1R)-trans-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate(compound 1) (yield: 66%).

n_(D) ²⁵ 1.5185 ¹ H-NMR (CDCl₃, internal standard TMS) δ value (ppm)1.17 (m, 3H), 1.39 (m, 3H), 1.42 (m, 1H), 1.70 (m, 6H), 2.12 (m, 4H),2.35 (m, 1H), 2.92 (m, 1H), 3.10 (q, 2H), 4.91 (m, 1H), 5.71 (brd,0.5H), 5.82 (brd, 0.5H) ¹⁹ F-NMR(CDCl₃, internal standard CCl₃ F) δvalue (ppm) -64.93 (t, 3H)

Preparation Example 4

To a mixed solution of 300 mg of(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxocyclopent-2-en-1-ol, 5 mg of2,6-di-tert-butyl-4-methylphenol, 178 mg of pyridine, 5 mg of4-dimethylaminopyridine and 10 ml of dried tetrahydrofuran, 400 mg of(2S)-2-(4-chlorophenyl)-methylbutanoic acid chloride was added dropwiseunder ice cooling, and the mixture was further reacted at roomtemperature for 6 hours. Thereafter, 10 ml of an aqueous 10% ammoniasolution was added to the reaction solution, followed by stirringvigorously for 2 hours. The reaction solution was extracted three timeswith diethyl ether and the layers were combined. Then, the combinedether layer was washed with saturated saline and dried over anhydrousmagnesium sulfate, and the solvent was distilled off under reducedpressure. The residue was subjected to silica gel column chromatography(eluent: mixture of n-hexane and ethyl acetate (30:1) containing 0.1%2,6-di-tert-butyl-4-methylphenol) to give 450 mg of(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxo-2-cyclopenten-1-yl(2S)-2-(4-chlorophenyl)-3-methylbutanoate (compound 16) (yield: 78%).

n_(D) ²⁴ 1.4989 ¹ H-NMR (CDCl₃, internal standard TMS) δ value (ppm)0.17 (m, 3H), 1.09 (m, 3H), 1.95 (d, 3H), 2.28 (m, 2H), 3.02 (m, 3H),3.20 (d, 1H), 5.78 (m, 1H), 7.28 (m, 4H) ¹⁹ F-NMR -64.91 (t, 3F)

Preparation Example 5

To a mixed solution of 300 mg of(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxocyclopent-2-en-1-ol, 5 mg of2,6-di-tert-butyl-4-methylphenol, 178 mg of pyridine, 5 mg of4-dimethylaminopyridine and 10 ml of dried tetrahydrofuran, 368 mg of(2S)-2-(4-fluorophenyl)-3-methylbutanoic acid chloride was addeddropwise under ice cooling, and the mixture was continuously reacted atroom temperature for 6 hours. Thereafter, 10 ml of an aqueous 10%ammonia solution was added to the reaction solution, followed bystirring vigorously for 2 hours. The reaction solution was extractedthree times with diethyl ether and the layers were combined. Then, thecombined ether layer was washed with saturated saline and dried overanhydrous magnesium sulfate, and the solvent was distilled off underreduced pressure. The residue was subjected to silica gel columnchromatography (eluent: mixture of n-hexane and ethyl acetate (30:1)containing 0.1% 2,6-di-tert-butyl-4-methylphenol) to give 400 mg of(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxo-2-cyclopenten-1-yl(2S)-2-(4-fluorophenyl)-3-methylbutanoate (compound 70) (yield: 73%).

n_(D) ²⁴ 1.4819 ¹ H-NMR (CDCl₃, internal standard TMS) δ value (ppm)0.78 (m, 3H), 1.09 (m, 3H), 1.95 (d, 3H), 2.81 (m, 2H), 3.01 (m, 3H),3.20 (d, 1H), 5.76 (m, 1H), 7.02 (m, 2H), 7.32 (m, 2H) ¹⁹ F-NMR (CDCl₃,internal standard CCl₃ F) -115.34 (s, 1F), -64.91 (t, 3F)

Examples of the present compound are shown in Tables 1 to 4, togetherwith their compound No. (respective substituents of the compoundrepresented by the formula I are shown).

In Tables 1 to 4, R₃ is represented by Q₁ to Q₂₇ described in theformulas XI and XII. ##STR11##

                  TABLE 1                                                         ______________________________________                                        Com-                    Optical                                               pound                   isomerism of  Isomerism                               No.   R.sub.1                                                                              R.sub.2    alcohol moiety                                                                         R.sub.3                                                                            of R.sub.3                              ______________________________________                                        1     CH.sub.3                                                                             CF.sub.3 CH.sub.2                                                                        RS       Q.sub.1                                                                            (1R)-trans                              2     H      CF.sub.3 CH(CH.sub.3)                                                                    RS       Q.sub.1                                                                            (1R)-cis, trans                         3     CH.sub.3                                                                             CF.sub.3 CF.sub.2                                                                        RS       Q.sub.1                                                                            (1R)-trans                              4     H      CF.sub.3 CH(CH.sub.3)                                                                    RS       Q.sub.2                                                                            (1R)-trans                              5     CH.sub.3                                                                             CF.sub.3 CH.sub.2                                                                        RS       Q.sub.2                                                                            (1R)-trans                              6     H      CF.sub.3 CH(CH.sub.3)                                                                    RS       Q.sub.3                                                                            (1RS)-cis-(Z)                           7     CH.sub.3                                                                             CF.sub.3 CH.sub.2                                                                        RS       Q.sub.4                                                                            (1RS)-cis, trans                        8     CH.sub.3                                                                             CF.sub.3 CH.sub.2                                                                        RS       Q.sub.5                                                                            (1R)-trans                              9     CH.sub.3                                                                             CF.sub.3 CH.sub.2                                                                        RS       Q.sub.6                                                                            --                                      10    CH.sub.3                                                                             CF.sub.3 CH.sub.2                                                                        RS       Q.sub.7                                                                            (1RS)-trans                             11    CH.sub.3                                                                             CF.sub.3 CF.sub.2                                                                        RS       Q.sub.2                                                                            (1R)-trans                              12    H      CF.sub.3 CH(CH.sub.3)                                                                    RS       Q.sub.6                                                                            --                                      13    CH.sub.3                                                                             CF.sub.3 CH.sub.2                                                                        RS       Q.sub.8                                                                            (1R)-trans                              14    CH.sub.3                                                                             CF.sub.3 CF.sub.2                                                                        RS       Q.sub.7                                                                            (1RS)-trans                             15    CH.sub.3                                                                             FCH.sub.2 CH.sub.2                                                                       RS       Q.sub.1                                                                            (1R)-trans                              16    CH.sub.3                                                                             CF.sub.3 CH.sub.2                                                                        RS       Q.sub.9                                                                            (S)                                     17    CH.sub.3                                                                             CF.sub.3 CH.sub.2                                                                        RS       Q.sub.10                                                                           (1R)-trans(EZ)                          18    CH.sub.3                                                                             CF.sub.3 CH.sub.2                                                                        RS       Q.sub.11                                                                           (1R)-trans                              19    CH.sub.3                                                                             CF.sub.3 CH.sub.2                                                                        RS       Q.sub.5                                                                            (1R)-trans                              ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                        20    CH.sub.3 FCF.sub.2 CH.sub.2                                                                      RS    Q.sub.5                                                                             (1R)-cis                                 21    CH.sub.3 FCF.sub.2 CH.sub.2                                                                      RS    Q.sub.1                                                                             (1R)-cis, trans                          22    CH.sub.3 FCF.sub.2 CH.sub.2                                                                      RS    Q.sub.7                                                                             (1R)-trans                               23    CH.sub.3 CF.sub.3 CH.sub.2 CH.sub.2                                                              RS    Q.sub.1                                                                             (1R)-trans                               24    CH.sub.3 CF.sub.3 CH.sub.2                                                                       RS    Q.sub.12                                                                            (1R)-trans                               25    CH.sub.3 CF.sub.3 CH.sub.2                                                                       RS    Q.sub.13                                                                            (1R)-cis(E)                              26    CH.sub.3 CF.sub.3 CH.sub.2                                                                       RS    Q.sub.14                                                                            (1R)-trans                               27    CH.sub.3 CF.sub.3 CF.sub.2                                                                       RS    Q.sub.6                                                                             --                                       28    CH.sub.3 CF.sub.3 CH.sub.2                                                                       RS    Q.sub.15                                                                            (1R)-cis(E)                              29    CH.sub.3 CF.sub.3 CF.sub.2                                                                       RS    Q.sub.10                                                                            (1R)-cis(E/Z)                            30    CH.sub.3 CF.sub.3 CH.sub.2                                                                       RS    Q.sub.16                                                                            (1R)-trans                               31    CH.sub.3 CF.sub.3 CH.sub.2                                                                       RS    Q.sub.17                                                                            (1R)-cis(E)                              32    CH.sub.3 CF.sub.3 CH.sub.2                                                                       RS    Q.sub.1                                                                             (1R)-cis, trans                          33    CH.sub.3 CF.sub.3 CF.sub.2                                                                       RS    Q.sub.1                                                                             (1R)-cis, trans                          34    CH.sub.3 F.sub.2 CHCH.sub.2                                                                      RS    Q.sub.10                                                                            (1R)-trans(E/Z)                          35    CH.sub.3 CF.sub.3 CH.sub.2                                                                       RS    Q.sub.18                                                                            (1RS)-cis, trans                         36    CH.sub.3 FCH.sub.2 CH.sub.2                                                                      RS    Q.sub.2                                                                             (1R)-trans                               37    CH.sub.3 F.sub.2 CHCH.sub.2                                                                      RS    Q.sub.1                                                                             (1R)-cis, trans                          ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        38    CH.sub.3 CF.sub.3 CH.sub.2                                                                        RS    Q.sub.19                                                                            (1R)-cis(E)                             39    CH.sub.3 CF.sub.3 CH.sub.2                                                                        RS    Q.sub.20                                                                            (1R)-cis(E)                             40    CH.sub.3 CF.sub.3 CH.sub.2                                                                        RS    Q.sub.21                                                                            (1R)-cis(E)                             41    CH.sub.3 CF.sub.3 CH.sub.2                                                                        RS    Q.sub.22                                                                            (1R)-trans(Z)                           42    CH.sub.3 CF.sub.3 CH.sub.2                                                                        RS    Q.sub.23                                                                            (1R)-cis(E)                             43    CH.sub.3 F.sub.2 CHCH.sub.2                                                                       RS    Q.sub.6                                                                             --                                      44    CH.sub.3 FCH.sub.2 CH.sub.2                                                                       RS    Q.sub.6                                                                             --                                      45    CH.sub.3 CF.sub.3 CH.sub.2                                                                        RS    Q.sub.3                                                                             (1R)-cis(E)                             46    CH.sub.3 F.sub.2 CHCH.sub.2                                                                       RS    Q.sub.2                                                                             (1R)-trans                              47    CH.sub.3 CF.sub.3 CH.sub.2 CH.sub.2                                                               RS    Q.sub.6                                                                             --                                      48    CH.sub.3 CF.sub.3 CF.sub.2                                                                        RS    Q.sub.3                                                                             (1R)-cis(Z)                             49    CH.sub.3 CF.sub.3 CF.sub.2                                                                        RS    Q.sub.12                                                                            (1R)-trans                              50    CH.sub.3 F(CH.sub.2).sub.3                                                                        RS    Q.sub.1                                                                             (1R)-trans                              51    CH.sub.3 F.sub.2 CHCH.sub.2 CH.sub.2                                                              RS    Q.sub.1                                                                             (1R)-trans                              52    CH.sub.3 F(CH.sub.2).sub.3                                                                        RS    Q.sub.6                                                                             --                                      53    CH.sub.3 F.sub.2 CHCH.sub.2 CH.sub.2                                                              RS    Q.sub.6                                                                             --                                      54    CH.sub.3 CF.sub.3 CH.sub.2 CH.sub.2                                                               RS    Q.sub.2                                                                             (1R)-trans                              55    CH.sub.3 F.sub.2 CHCH.sub.2                                                                       RS    Q.sub.7                                                                             (1R)-trans                              56    CH.sub.3 CF.sub.3 CH.sub.2 CH.sub.2                                                               RS    Q.sub.10                                                                            (1R)-trans(E/Z)                         57    CH.sub.3 CF.sub.3 CH.sub.2 CH.sub.2                                                               RS    Q.sub.7                                                                             (1R)-trans                              58    CH.sub.3 F.sub.2 CHCH.sub.2                                                                       RS    Q.sub.5                                                                             (1R)-trans                              59    H        CF.sub.3 CH(CH.sub.3)                                                                    RS    Q.sub.12                                                                            (1R)-trans                              ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        60    H        CF.sub.3 CH(CH.sub.3)                                                                    RS    Q.sub.1                                                                             (1R)-cis, trans                         61    CH.sub.3 CF.sub.3 CF.sub.2 CF.sub.2                                                               RS    Q.sub.6                                                                             --                                      62    CH.sub.3 F(CH.sub.2).sub.3                                                                        RS    Q.sub.2                                                                             (1R)-trans                              63    CH.sub.3 CF.sub.3 CH.sub.2                                                                        RS    Q.sub.24                                                                            (1R)-cis                                64    CH.sub.3 CF.sub.3 CH.sub.2                                                                        RS    Q.sub.25                                                                            (1R)-trans(E/Z)                         65    CH.sub.3 CF.sub.3 CF.sub.2                                                                        RS    Q.sub.13                                                                            (1R)-cis(Z)                             66    CH.sub.3 CF.sub.3 CH.sub.2 CH.sub.2                                                               RS    Q.sub.5                                                                             (1R)-trans                              67    CH.sub.3 CF.sub.3 CH.sub.2                                                                        RS    Q.sub.20                                                                            (1R)-trans(E)                           68    CH.sub.3 CF.sub.3 CH.sub.2                                                                        RS    Q.sub.17                                                                            (1R)-trans(E)                           69    CH.sub.3 CF.sub.3 CH.sub.2                                                                        RS    Q.sub.26                                                                            (1R)-trans(E)                           70    CH.sub.3 CF.sub.3 CH.sub.2                                                                        RS    Q.sub.27                                                                            (1R)-S                                  71    CH.sub.3 CF.sub.3 CF.sub.2                                                                        RS    Q.sub.24                                                                            (1R)-cis                                72    H        CF.sub.3 CH(CH.sub.3)                                                                    RS    Q.sub.24                                                                            (1R)-cis                                73    CH.sub.3 CICH.sub.2 CH.sub.2                                                                      RS    Q.sub.2                                                                             (1R)-trans                              74    CH.sub.3 CIF.sub.2 CCH.sub.2                                                                      RS    Q.sub.2                                                                             (1R)-trans                              ______________________________________                                    

Next, some physical properties of examples of the present compound willbe described.

Compound No.

1 n_(D) ²² 1.5185

5 n_(D) ²⁵ 1.4915

9 n_(D) ²⁵ 1.4621

16 n_(D) ²² 1.4989

70 n_(D) ²⁴ 1.4819

Next, Production Example of the alcohol compound represented by theformula VII will be described.

Production Example of intermediate

To 98.8 g of ethyl 4,4,4-trifluorobutyrylacetate 250 ml of an aqueous10% sodium hydroxide solution was added, and the resulting mixture wasstirred vigorously for 12 hours. After adjusting the pH of the reactionsolution to 7.5 by adding an aqueous 10% sulfuric acid solution, 250 mlof toluene, 2.86 g of sodium bicarbonate and 6.43 g of hydrosulfite wereadded under a nitrogen flow, followed by heating to 37° C. To themixture, 90 g of methyl glyoxal was added dropwise over one hour and thereaction was conducted for additional 12 hours. To the reactionsolution, 50 g of sodium chloride was added, and the mixture wasextracted three time with ethyl acetate. The ethyl acetate layers werecombined and, after drying over anhydrous magnesium sulfate, the solventwas distilled off under reduced pressure.

To the residue, 450 ml of an aqueous 5% sodium hydroxide solution wasadded under ice cooling, and the mixture was stirred vigorously for 5hours. After adjusting the pH of the reaction solution to 7.3 by addingan aqueous 10% hydrochloric acid solution, the solution was extractedthree times with ethyl acetate. The layers were combined and thecombined ethyl acetate layer was dried over anhydrous magnesium sulfate,and the solvent was distilled under reduced pressure. The residue wasdistilled off under reduced pressure to give 45 g of the objective(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxocyclopent-2-en-1-ol (b.p.100°-133° C., 0.52 mmHg) (yield: 50%).

¹ H-NMR (CDCl₃, internal standard TMS) δ value (ppm): 2.19 (s, 3H), 2.35(dd, 1H), 2.35 (dd, 1H), 3.08 (q, 2H), 4.82 (br, 1H) ¹⁹ F-NMR (CDCl₃,CCl₃ F inner standard) δ value (ppm): -65.1 (t, 3F)

Next, Production Examples of the compounds [V] to [VIII] shown in thereaction scheme X will be described.

REFERENCE PRODUCTION EXAMPLE (1) Production Example of compound [V]

To 160 g of ethyl 4,4,4-trifluorobutyrate, a mixed solution of 123 g ofpotassium hydroxide, 900 ml of methanol and 80 ml of water was addedunder ice cooling and the mixture was further reacted at roomtemperature for 12 hours. After the reaction solution was concentratedunder reduced pressure, the resulting residue was then partitionedbetween water and diethyl ether. The ether layer was extracted once withwater and the water layer was combined with the aqueous layer which hadalready been partitioned. After adjusting the pH to about 1 by theaddition of an aqueous 10% ice-cooled hydrochloric acid solution, themixture was extracted three times with diethyl ether. The layers werecombined and the Combined ether layer was washed twice with saturatedsaline and dried over anhydrous magnesium sulfate. Then, the solvent wasdistilled off under reduced pressure to give 131 g of4,4,4-trifluorobutyric acid (yield: 98%).

¹ H-NMR (CDCl₃, internal standard TMS) δ value (ppm): 2.52 (m, 2H), 2.67(t, 2H)

(2) Production Example of compound [VI]

To a mixture of 131 g of 4,4,4-trifluorobutyric acid and 1 liter ofpentane, 101 ml of oxalyl chloride and 0.1 ml of dimethylformamide wereadded, and the mixture was heated at reflux for 3 hours. The reactionsolution was distilled at normal pressure to give 112 g of4,4,4-trifluorobutyryl chloride (b.p. 103° C., 760 mmHg) (yield: 76%).

(3) Production Example of compound [VII]

To a mixture of 20.35 g of magnesium (turning) and 148 ml of ethanol,0.1 ml of carbon tetrachloride was added and heated to 55° C. To themixture, a mixed solution of 197 ml of ethanol, 700 ml of diethyl etherand 168 g of diethyl malonate was added dropwise over one hour. After 2hours, the reaction solution was cooled to -5° C. under a nitrogen flowand 112 g of 4,4,4-trifluorobutyryl chloride was added. After thetemperature was returned to ambient temperature over one hour, thereaction was further conducted for 12 hours. The reaction solution waspoured into an aqueous 5% ice-cooled hydrochloric acid, and extractedthree times with diethyl ether. The layers were combined and thecombined ether layer was washed twice with saturated saline and driedover anhydrous magnesium sulfate. Then, the solvent was distilled offunder reduced pressure to give 179 g of 4,4,4-trifluorobutyryl-malonicacid diethyl ester (b.p.: 125°-134° C., 15 mmHg) (yield: 90%).

¹ H-NMR (CDCl₃, internal standard TMS) δ value (ppm): 1.32 (t, 3H), 2.50(m, 2H), 2.95 (t, 2H), 4.29 (q, 2H), 4.50 (s, 1H)

(4) Production Example of compound [VIII]

A mixture of 179 g of 4,4,4-trifluorobutyrylmalonic acid diethyl ester260 ml of water and 322 mg of paratoluenesulfonic acid was stirredvigorously for 6 hours while heating at reflux for 6 hours. The reactionsolution was poured into an aqueous saturated sodium bicarbonate, andextracted three times with diethyl ether. The layers were combined, andthe combined ether layer was washed with saturated saline and dried overanhydrous magnesium sulfate. Then, the solvent was distilled off underreduced pressure and the residue was distilled under reduced pressure togive 98.8 g of ethyl 4,4,4-trifluorobutyryl acetate (b.p. 93°-97° C., 15mmHg) (yield: 74%).

¹ H-NMR (CDCl₃, internal standard TMS) δ value (ppm): 1.28 (t, 3H), 2.45(m, 2H), 2.96 (t, 2H), 3.48 (s, 2H), 4.22 (q, 2H)

Next, Formulation Examples will be described. Further, all "parts" areby weight and the present compounds are represented by the compound Nos.described in Tables 1 to 4.

Formulation Example 1

Emulsifiable concentrates

20 parts of each of the compounds (1) to (74) are separately dissolvedin 65 parts of xylene. Each of the obtained mixtures is mixed with 15parts of an emulsifier Solpol 3005X (trade name by Toho Kagaku Co.,Ltd.), and stirred sufficiently to give 20% emulsifiable concentrate foreach compound.

Formulation Example 2

Wettable powders

To 40 parts of each of the compounds (1) to (74), 5 parts of Solpol3005X (same as above) is added, and stirred sufficiently. Then, 32 partsof Carplex #80 (trade name by Shionogi Seiyaku Co., Ltd, synthetichydrated siliconoxide fine powder) and 23 parts of 300-mesh diatomaceousearth are added to the mixture, which is stirred with a mixer to give40% emulsifiable concentrate for each compound.

Formulation Example 3

Granules

1.5 parts of each of the compounds (1) to (74) is sufficiently mixedwith 98.5 parts of AGSORBLVM-MS 24/48 (granular carrier of calcinedmontmorillonite having a particle diameter of 24 to 48 meshes,manufactured by OIL DRI Co.) to give 1.5% granule for each compound.

Formulation Example 4

Microcapsules

10 parts of each of the compounds (1) to (74) is sufficiently mixed with10 parts of phenylxylylethane and 0.5 part of Sumijule L-75 (tolylenediisocyanate manufactured by Sumitomo Bayer Urethane Co., Ltd.) and themixture is added in 20 parts of an aqueous 10% solution of gum arabic,followed by stirring with a homomixer to give an emulsion of 20 μm inaverage particle size. Then, 2 parts of ethyleneglycol are added to theemulsion and the mixture is reacted in a hot bath at 60° C. for 24 hoursto give a micro-capsule slurry.

On the other hand, 0.2 part of Xanthan gum and 1.0 part of Veegum R(aluminum magnesium silicate manufactured by Sanyo Kasei Co., Ltd.) aredispersed in 56.3 parts of deionized water to give a thickener solution.

42.5 parts of the above microcapsule slurry is mixed with 57.5 parts ofthe thickener solution to give 10% microcapsule for each compound.

Formulation Examples 5

Flowables

10 parts of each of the compounds (1) to (74) is sufficiently mixed with10 parts of phenylxylylethane, and the mixture is added in 20 parts ofan aqueous 10% solution of polyethyleneglycol, followed by stirring witha homomixer to give an emulsion of 3 μm in average particle size.

On the other hand, 0.2 part of Xanthan gum, 1.0 part of Veegum R(aluminum magnesium silicate manufactured by Sanyo Kasei Co., Ltd.) aredispersed in 58.8 parts of deionized water to give a thickener solution.

40 parts of the above emulsion are mixed with 60 parts of the thickenersolution to give 10% flowable for each compound.

Formulation Example 6

Dusts

5 parts of each of the compounds (1) to (74) is separately mixed with 3parts of Carprex #80 (same as above), 0.3 part of PAP and 91.7 parts of300 mesh talc, and each of the obtained mixture is stirred with a mixerto give 5% dust for each compound.

Formulation Example 7

Oil solutions

0.1 part of each of the compounds (1) to (74) is separately dissolved in5 parts of dichloromethane, and each of the solution is mixed with 94.9parts of deodorized kerosine to give 1.0% oil solution for eachcompound.

Formulation Example 8

Oil-based aerosol

One part of each of the compounds (1) to (74), 5 parts ofdichloromethane are dissolved in 34 parts of deodorized kerosine, and anaerosol vessel is filled with the solution. Then, the vessel is equippedwith a valve, through which 60 parts of a propellent (liquefiedpetroleum gas) are charged under pressure to give an oil-based aerosolfor each compound.

Formulation Example 9

Water-based aerosol

An aerosol vessel is filled with 50 parts of pure water and a mixture of0.6 part of each of the compounds (1) to (74), 5 parts of xylene, 3.4parts of deodorized kerosine and 1 part of an emulsifier (ATMOS 300(trade name by Atlas Chemical Co.)). Then, the vessel is equipped with avalve, through which 40 parts of a propellent (liquefied petroleum gas)are charged under pressure to give a water-based aerosol for eachcompound.

Formulation Example 10

Mosquito-coils

0.3 part of each of the compounds (1) to dissolved in 20 ml of acetone,and the solution is mixed uniformly with 99.7 g of a carrier formosquito-coil (prepared by mixing a flour of Machilus thunbergii Sieb.et Zucc., a pyrethrum marc and a wood flour in a proportion of 4:3:3)with stirring. Then, 120 ml of water is added to the mixture, which iskneaded sufficiently, molded and dried to give a mosquito-coil of eachcompound.

Formulation Example 11

Mosquito-mat for electric heating fumigation

0.8 g of each of the compounds (1) to (74) and 0.4 g of piperonylbutoxide are each dissolved in acetone to make 10 ml of a solution. Asubstrate for the mat of electric heating formulations having a size of2.5 cm×1.5 cm×0.3 cm in thickness (prepared by forming a fibrillatedmixture of cotton linter and pulp into a sheet) is impregnated uniformlywith 0.5 ml of the solution to give a mosquito-mat for electric heatingfumigation of each compound.

Formulation Example 12

Solutions for electric heating fumigation

3 parts of each of the compounds (1) to (74) is separately dissolved in97 parts of deodorized kerosine, and the solution was charged in avessel made of vinyl chloride. Then, a core for absorbing solution(prepared by solidifying inorganic powder using a binder, followed bysintering), of which top part can be heated with a heater, is insertedto give a solution for electric heating fumigation of each compound.

Formulation Example 13

Heating smoke formulations

100 mg of each of the compounds (1) to (74) is separately dissolved in asuitable amount of acetone, and a porous ceramic plate having a size of4.0 cm×4.0 cm×1.2 cm in thickness is impregnated with the resultingsolution to give heating smoke formulation of each compound.

Formulation Example 14

Volatile agent

One hundred μg of each of the compounds (1) to (74) is separatelydissolved in a suitable amount of acetone and the solution is uniformlyapplied on a filter paper having a size of 2 cm×2 cm×0.3 mm inthickness, and then acetone is air-dried to give a volatile agent ofeach compound.

Formulation Example 15

Mite-repellent sheet

A filter paper is impregnated with an acetone solution of each of thecompounds (1) to (74) so that the amount of the compound to beimpregnated is 1 g/m², and acetone is air-dried to give a mite-repellentsheet of each compound.

The following Test Examples illustrate that the present compounds areuseful as an active ingredient of an agent for controlling noxiousorganisms. Further, the present compounds are shown by the compound Nos.in Tables 1 to 4 and the compound [(RS)-isomer on the alcohol side,(1R)-cis, trans-isomer on the acid side] used for comparison is shown bythe symbols in Table 5.

                  TABLE 5                                                         ______________________________________                                        Symbol of                                                                     chemical                                                                      structural                                                                           Compound formula   Remarks                                             ______________________________________                                                ##STR12##         d-Allethrin (commercially available insecticide)    ______________________________________                                    

Test Example 1

Insecticidal test against larvae of Spodoptera litura

An emulsifiable concentrate was prepared from the test compoundaccording to Formulation Example 1. Then, 13 g of an artificial diet forSpodoptera litura, prepared in a polyethylene cup having a diameter of11 cm in advance, was impregnated with 2 ml of a solution of theemulsifiable concentrate diluted with water (500 ppm). Ten fourth instarlarvae of Spodoptera litura were set free in the cup. After six days,the survival of larvae was examined to determine the mortality. Theresults are shown in Table 6.

                  TABLE 6                                                         ______________________________________                                        Compound No.       Mortality (%)                                              ______________________________________                                        1                  100                                                        5                  100                                                        9                  80                                                         Emulsifiable concentrate                                                                         0                                                          containing no active ingredient                                               ______________________________________                                    

Test Example 2

Insecticidal test against larvae of Nilaparvata lugens

A rice stalk (about 5 cm in length) was dipped in an aqueous dilutedsolution of an emulsifiable concentrate (500 ppm) of the test compoundprepared according to Formulation Example 1 for 1 minute. After airdrying, the rice stalk was placed in a polyethylene cup of 5.5 cm indiameter wherein a filter paper containing water (1 ml) (5.5 cm indiameter) is put on the bottom. Then, about 30 larvae of Nilaparvatalugens were set free in the cup. After six days, the survival of larvaewas examined to determine the mortality. The effect was evaluatedaccording to the following criteria.

a: No survival larvae are observed.

b: Five survival larvae or less are observed.

c: Six survival larvae or more are observed.

The results are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                        Compound No.       Judgment of effect                                         ______________________________________                                        1                  a                                                          5                  a                                                          9                  a                                                          Emulsifiable concentrate                                                                         c                                                          containing no active ingredient                                               ______________________________________                                    

Test Example 3

Insecticidal test against Musca domestica

A filter paper of 5.5 cm in diameter was put on the bottom of apolyethylene cup of 5.5 cm in diameter and 0.7 ml of an aqueous dilutedsolution of an emulsifiable concentrate (500 ppm), prepared from thetest compound according to Formulation Example 1 was dropped and,further, about 30 mg of sucrose as a bait was uniformly charged in thecup. Then, 10 female adults Musca domestica having low sensitivity topyrethroid were set free in the cup, and a cap was put on the cup. Afterone day, the survival of female adults was examined to determine themortality. The results are shown in Table 8.

                  TABLE 8                                                         ______________________________________                                        Compound No.       Mortality (%)                                              ______________________________________                                        1                  100                                                        5                  100                                                        9                  90                                                         A                  10                                                         Emulsifiable concentrate                                                                         0                                                          containing no active ingredient                                               ______________________________________                                    

Test Example 4

Ten adults Blattella germanica (5 male adults and 5 female adults) werereleased in a polyethylene cup of 9 cm in diameter of which wall surfacewas applied with vaseline thinly and the cup was covered with a 16-meshnylon net and, further, the covered cup was placed at the bottom of aplastic cylinder (10 cm in inner diameter×37 cm in height). Then, 0.6 mlof each 0.1% (w/w) oil solution of the present compound obtained inFormulation Example 7 was directly sprayed from the top of the cylinder,using a spray gun at a pressure of 0.6 atm. After 5 minutes, the rate ofknocked-down adults was examined. The results are shown in Table 9.

                  TABLE 9                                                         ______________________________________                                        Compound No.      Knocked-down ratio (%)                                      ______________________________________                                        5                 90                                                          9                 80                                                          A                 40                                                          Emulsifiable concentrate                                                                        0                                                           containing no active ingredient                                               ______________________________________                                    

Test Example 5

Ten female adults Culex pipiens pallens were released in a cubic glasschamber having a side of 70 cm(0.34 m³). Then, both ends of a 0.3% (w/w)mosquito coil (1.0 g) of the present compound prepared according toFormulation Example 10 was lit and then placed in the glass chamber.After 8.5 minutes, the rate of knocked-down adults was examined. Theresults are shown in Table 10.

                  TABLE 10                                                        ______________________________________                                        Compound No.      Knocked-down ratio (%)                                      ______________________________________                                        5                 70                                                          9                 90                                                          A                 10                                                          ______________________________________                                    

Test Example 6

Insecticidal test against Culex pipiens pallens

An emulsifiable concentrate was made from the test compound according toFormulation Example 1 and the resulting emulsifiable concentrate wasdiluted with water, and 0.7 ml of the diluted solution was added to 100ml of deionized water (concentration of active ingredient: 3.5 ppm).Then, 20 heads of final instar larvae of Culex pipiens pallens were setfree therein. After one day, the survival of larvae was examined.

The effect was evaluated according to the following criteria.

a: Mortality of 90% or more

b: Mortality of 10 or more and less than 90%

c: Mortality of less than 10%

The results are shown in Table 11.

                  TABLE 11                                                        ______________________________________                                        Compound No.       Judgment of effect                                         ______________________________________                                        1                  a                                                          5                  a                                                          9                  a                                                          16                 a                                                          70                 a                                                          Emulsifiable concentrate                                                                         c                                                          containing no active ingredient                                               ______________________________________                                    

Test Example 7

Insecticidal test against larvae of Diabrotica undecimpunctata howardi

A filter paper of 5.5 cm in diameter was put on the bottom of apolyethylene cup of 5.5 cm in diameter and 1 ml of an aqueous dilutedsolution of an emulsifiable concentrate (50 ppm) of the test compoundprepared according to Formulation Example 1 was dropped on the filterpaper. Then, about 30 eggs of Diabrotica undecimpunctata howardi wereplaced on the filter paper and one sprout corn as a bait was charged inthe cup. After 8 days, the survival of hatched larvae was examined. Theeffect was evaluated according to the following criteria.

a: Mortality of 100%

b: Mortality of 90% or more and less than 99%

c: Mortality of less than 90%

The results are shown in Table 12.

                  TABLE 12                                                        ______________________________________                                        Compound No.       Judgment of effect                                         ______________________________________                                        1                  a                                                          5                  a                                                          9                  a                                                          16                 a                                                          70                 a                                                          Emulsifiable concentrate                                                                         c                                                          containing no active ingredient                                               ______________________________________                                    

Test Example 8

0.64 MI of 0.25% (w/v) solution of the test compound diluted withacetone was dropped on an aluminum dish of which diameter of the bottompart is 7 cm, and the acetone was air-dried. Then, 20 female adults ofCSMA Musca domestica were set free in a polyethylene cup (9 cm indiameter×4.5 cm in height) and the top was covered with a 16 mesh nylonnet so that the insects do not contact directly with the surface treatedwith the drug. This cup was placed upside down on the aluminum dish and,after 60 minutes at 25° C., the rate of knocked-down adults wasexamined. The results are shown in Table 13.

                  TABLE 13                                                        ______________________________________                                        Compound No. Knocked-down ratio (%)                                           ______________________________________                                        1            100                                                              5            90                                                               9            100                                                              A            0                                                                No treatment 0                                                                ______________________________________                                    

Experiment Example 9

A mite-repellent sheet prepared according to Formulation Example 15 wascut into a circle of 4 cm in diameter, and about 50 Dermatophagoidesfarinae were released on the surface of the filter paper. After one day,the number of mites, which were dead or trapped by an adhesive substanceapplied on the circumference of the sheet for preventing escape, wascounted. The total of the dead or trapped mites was evaluated as aneffective controlling value. The results are shown in Table 14.

                  TABLE 14                                                        ______________________________________                                        Compound No.  Controlling ratio (%)                                           ______________________________________                                        1             100                                                             5             100                                                             9             100                                                             No treatment  7                                                               ______________________________________                                    

What is claimed is:
 1. An ester compound represented by the formula I:##STR13## wherein R₁ is a methyl group or a hydrogen atom; R₂ is a C₂-C₄ alkyl group substituted with a fluorine atom or atoms; and R₃ is apyrethroid acid residue.
 2. The ester compound according to claim 1,wherein R₃ is a group of the formula II: ##STR14## wherein Z₁ is ahydrogen atom or a methyl group; and Z₂ is a hydrogen atom, a C₁ -C₆alkyl group which may be substituted with a halogen atom or atoms, a C₁-C₆ alkoxy group which may be substituted with a halogen atom or atoms,a (C₁ -C₆ alkoxy)methyl group which may be substituted with a halogenatom or atoms, a (C₁ -C₆ alkoxy)ethyl group which may be substitutedwith a halogen atom or atoms, a C₂ -C₄ alkenyloxy group which may besubstituted with a halogen atom or atoms, a C₂ -C₄ alkynyloxy groupwhich may be substituted with a halogen atom or atoms, a (C₂ -C₄alkenyl)oxymethyl group which may be substituted with a halogen atom oratoms, or a (C₂ -C₄ alkynyl)oxymethyl group which may be substitutedwith a halogen atom or atoms;Z₂ is a group of the formula III: ##STR15##wherein Z₃ is a hydrogen atom or a halogen atom; and T₁ and T₂ are thesame or different and each indicate a hydrogen atom, a halogen atom, aC₁ -C₃ alkyl group which may be substituted with a halogen atom oratoms, a cyano group, a phenyl group which may be substituted with ahalogen atom or atoms, a (C₁ -C₄ alkoxy)carbonyl group which may besubstituted with a halogen atom or atoms; or T₁ and T₂ bond each otherat their terminal and indicate a C₃ -C₆ cycloalkyl group Z₂ is a groupof the formula IV: ##STR16## wherein B is an oxygen atom or a sulfuratom; Z₂ is a group of the formula V: ##STR17## wherein D is a hydrogenatom or a halogen atom: and G is a C₁ -C₆ alkyl group which may besubstituted with a halogen atom or atoms, a C₃ -C₅ cycloalkyl group or aphenyl group which may be substituted with a halogen atom or atoms; orR₃ a group of the formula VI: ##STR18## wherein J is a halogen atom, aC₁ -C₆ alkyl group which may be substituted with a halogen atom or atomsor a C₁ -C₆ alkoxy group which may be substituted with a halogen atom oratoms.
 3. An estercompound:(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxo-2-cyclopenten-1-yl(1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate,(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxo-2-cyclopenten-1-yl-2,2,3,3-tetramethylcyclopropanecarboxylate,(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxo-2-cyclopenten-1-yl(1R)-trans-2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropanecarboxylate,(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxo-2-cyclopenten-1-yl(2S)-2-(4-chlorophenyl)-3-methylbutanoate or(RS)-2-methyl-3-(2,2,2-trifluoroethyl)-4-oxo-2-cyclopenten-1-yl(2S)-2-(4-fluorophenyl)-3-methylbutanoate.
 4. An agent for controllingnoxious organisms, comprising the ester compound of claim 1 as an activeingredient.
 5. A method for controlling noxious organisms, whichcomprises applying an effective amount of the ester compound of claim 1.6. An ester compound according to claim 2, wherein R₂ is a2,2,2-trifluoroethyl group, a 2,2-difluoroethyl group, apentafluoroethyl group, a 2-fluoroethyl group or a 3-fluoropropyl group.7. A process for producing the ester compound of the formula I asclaimed in claim 1, which comprises reacting an alcohol compound of theformula VII: ##STR19## wherein R₁ and R₂ are the same as defined inclaim 1 with a carboxylic acid of the formula VIII:

    R.sub.3 --COOH

wherein R₃ is the same as defined in claim 1 in the presence of adehydrating agent, or its reactive derivative in the presence of a base.